Dyestuffs of the methine series



Patented A rtzl, 1942 UNITED :STATESL PATENT: i

DYESTUFFS OFFHE METH INE SERI ES a Werner Miiller, Cologne, and CarlBerres', Leverkusen-Wiesdorf, Germany, assignors to General Aniline &Film Corporation, a corporation of Delaware v i N 0 Drawing. ApplicationAugust 1, 1939, Serial No. 287,750. In Germany Apri1 26, 1935 1 Claim.(01. 260-240) The present invention relates to new dyestuffs, moreparticularly it relates to dyestuffs of the The invention isillustratedby the following examples, without being restricted thereto,the

methine series which may berepresented by the parts being by weight:general formula: I

Example 1 In the saidformula It stands forialkyl or laydroxyalkyl, R1stands forhydrogen, hydroxyalkyl, o

containing a reactive methyl or methylene group bound to. a nucleus, inwhich the;C portion is formed from the said reactivej'group andthewhereinR and R1 mean the same as" stated above, As far as thesealdehydesare not yet 55 known they can be prepared e. g. according to the vprocess described in U. S; Patent 2,141,090, or in a manner analogous tothat described in British specification No; 17,135 of 1898, or accordingto the method-described in Berichte der Deutschen ChemischenGesellschaft, vol. 60, p. 119.

As suitable compounds with reactive methyl or methylene groups bound toanucleus there may be mentioned, for example pyrazolones, indolines,alpha-methylindolines, alphaand gamma-alkylpyridines, alkylquinoline,oxythionaphthene, di-

ketohydrindene, acetophen'one, dinitrotoluene and soon. t I

In this manner, new and'very clear basic dyestuffs are obtainable, whichaccording to the components employed, are suited for different purposes,as for instance for dyeing of cellulose ethers and esters, for themanufacture of beautiful fast lakes on textiles and substrata; and alsoa as leather dyestuffs.

17.9 parts of. p-N-hydroxyethyl-N-methylaminobenzaldehyde and 17.3 partsof 1.3.3-trimethyl- 2- methyleneindoline are dissolved in 35 parts ofglacial acetic acid and heated for several hours to 100 C. Thereupon thereaction mass is poured into water andthe dyestufiprecipitated I withsodium chloride. By redissolving the dyestuff from dilutesodiumjchloride solution it is obtained incrystals, showing abluesurface luster. The dyestu'ff corresponds to the following N groupformula:

.R t 9113 CH; R1 ,s l stands in para-position to V 9 '9 N The newdyestuffs are obtainable by condensing according the methods known perse a com- 25 pound with a reactive methyl or methylene group bound to anucleus with a para-aminoarylalde- E; hyde of the generalformulaa a R\ ny :m QH2.0H2.OH

I 'N-aryl-(y Y t I I I and dyes acetate artificial silk bright redshades of good fastness properties. On cotton mor Instead ofp-N-hydroxyethyl-N methylaminobenzaldehyd'e other aldehydes may be used.Thus with p N-hydroxyethyl-N-phenylaminobenzaldehyde a dyestuif of thefollowing formula is obtained which is very similar in its appearanceand its tinctorial properties to the above dyestufi. It yields onacetate artificial silk a little more bluish shades. Withp-N-dihydroxyethylaminobenzaldehyde a dyestufi is obtained dyeing clearred shades. Compared with the shades obtained of the correspondingdyestuff with p-N-hydroxyethyl-N-methyl-aminobenzaldehyde the shades aremore yellowish. It shows good tinctorial properties and corresponds tothe following formula The dyestufi withp-N-ethyl-N-benzylaminobenzaldehyde which corresponds to the followingformu CHa-C- l N-C Hz. CH2

is essentially more bluish than the first mentioned dyestufi, however,in its other properties very similar to it.

Example 2 In this Example 3 17 .9 parts ofp-N-hydroxyethyl-N-methylaminobenzaldehyde and 24.9 parts ofu-picolineeth-iodide are dissolved in parts of alcohol. Some pyridine isadded and the mixture is heated for several hours with reflux. Aftersome time, when the solution is still warmed, the dyestufi precipitatesin fine red crystals. When cold the crystals are sucked off and washedwith alcohol. The dyestuff corresponds to the following formula CzHsN-CHs CH2.CH1. OH

It is sufiiciently soluble in water and yields clear reddish yellowshades of good fastness to light and washing.

Instead of p-N-oxethyl-N-methylaminobenzaldehyde other aldehydes may beused. Thus with p-N-hydroXyethyl-N-butylaminobenzaldehyde a brickredcrystal powder is obtained which dyes acetate artificial silk clearyellow orange shades, being somewhat more reddish than those obtainedwith the above dyestufi. Otherwise it shows the same tinctorialproperties. It corresponds to the following formula III-C Hz. CH2. CH2.CH1 GHQ-CHLOE With pN-hydroxyethyl-N-benzylaminobenzaldehyde likewise acrystallized dyestuff is obtained which corresponds to the followingformula and dyes acetate artificial silk almost pure yellow shades andshows good fastness properties.

When using instead of a-picoline-eth-iodide quinaldine-eth-iodide andcondensing it with p- N-hydroxyethyl-N-methylaminobenzaldehyde in thesame manner. a dark brown crystal powder of the dyestufl' of theconstitution is obtained which dyes acetate artificial silk clear bluishred shades of very good fastness properties.

Example 4.

17.9 parts of p-N-hydroxyethyl-N-methylaminobenzaldehyde and 13.1 partsof a-methylindole (methylketole) aredissolved in 30 parts of glacialacetic acid and heated for several hours to 100 C. 'I'hereupon thereaction mass .is poured into water and salted out with sodium wchloride. The dyestuff precipitates as fine bluish violet crystalpowder. It is sucked off and washed with dilute sodium chloridesolution. The dyestufi corresponds to the following formula N -om omcmonis suificiently soluble in water and dyes acetate artificial silk clearred violet shades.

Example 5 17.9 parts of p-N-hydroxyethyl-N-methylaminobenzaldehyde andparts of oxythio naphthene are dissolved in 45 parts of alcohol.

A few drops of piperidine are added and the mixture heated for severalhours with reflux. After coolin the dyestufi separates as red crystalpowder. It is sucked ofi and washed with alcohol. The dyestuficorresponds. to the following formula l and dyes acetate artificial silkorange red shades of good fastness properties.

In the same way a dyestuff is prepared fromp-N-methyl-N-phenylaminobenzaldehyde a n d oxythionaphthene. It formsred crystals, melting and dyes acetate artificial silk red orange shadesof good fastness properties.

Example 6 17.9 parts of p-N-hydroxyethy1-N-methylaminobenzaldehyde and182' parts of 2.4-dinitrotoluene are mixedwith about 3 parts ofpiperidine and heated for several hours to C. Thereupon parts of alcoholare slowly run with stirring into the reaction mixture. The dyestuffprecipitates as dark greenish crystal powder. It is sucked on and washedwith alcohol. The dyestufi corresponds to the following formula IOH=CHONO1 N-CH:

CHa-CH2.0H

and. dyes acetate artificial silk brown red shades.

' Example 7 17.9 parts of P-N-hydroxyethyl-N-methylaminobenzaldehyde and12 parts of aoetophenone are dissolved in 35 parts of alcohol with theaddition of 2 drops of concentrated caustic soda lye and heated forseveral hours with reflux. The dyestulf is precipitated with water andseveral times digested with hot Water. The dyestuif corresponds to thefollowing formula N-CHI CHg.CH:.OH

and dyes acetate artificial silk bright yellow shades of very stronggreenish fluorescence.

Example 8 17.9 parts of p-N-hydroxyethyl-N-methylaminobenzaldehyde and17.4,parts of 1-phenyl-3- methyl-fi-pyrazoloneare dissolved in 45 partsof alcohol and heated for several hours with reflux. The formed dyestufiis precipitated with water and several times digested with hot water.With the same result the formation of the dyestufi can be-carried.through by heating the components in crystals melting at 152-453 C. Itcorresponds glacial acetic acid. The dyestuff corresponds to to thefollowing formula the following formula 01 CHa-C=N l CHs- 5 C o /NCH=C-C 0 on: c0

| N-CH: N-CHa cmonton and dyes acetate artificial silk bright orangeShades of good fastnass propertlesand is very similar to the precedingdyestuff in When replacing the p-N-hydroxyethyl-N- its tinctorialproperties methylam nobenzaldehyde by p-N-methyl-N- This application isin part a continuation of phenylammobenzaldehyde a dyestufi is obtainedour copending application serial Number 75226 which forms orangecrystals melting at 193- fil d April 18) 1935, now U. 5. Patent No. 79194 C. The dyestuffcorresponds to the follow- 895 dated 14) 9 ingformula We claim:

' 2D The dyestufi of the formula CHa-C=N CH 3 HaO-C 011:0-00 l CH=CH-CH2PO4 zHs I l I N-0Ha l NCH:

and dyes acetate artificial silk yellow orange shades of good fastnesspe ti dyeing acetate artificial silk deep v1olet shades Fromp-N-methyl-N-phenylaminobenzaldeof Very good fastness propertieshyde and1-(2-chlorophenyl)-3-methy1-5-pyra- WERNER L ER. zolone a dyestuff isobtained which forms red CARL BERRES.

